Chrome complexed azomethine dye

ABSTRACT

NOVEL METAL-COMPLEXED AZOMETHINE DYES WHICH ARE ALSO SILVER HALIDE DEVELOPING AGENTS, NOVEL NON-COMPLEXED AZOMETHINES USEFUL IN THE PREPARATION OF THE SAME, AND NOVEL PHOTOGRAPHIC SYSTEMS AND PROCEDURES EMPLOYING THE AFOREMENTIONED METAL COMPLEXES TO OBTAIN COLOR IMAGES, PARTICULARLY SYSTEMS AND PROCEDURES FOR PREPARING COLOR IMAGES BY DIFFUSION TRANSFER.

United States Patent CHROME COMPLEXED AZOMETHINE DYE Elbert M. Idelson,Newton, Mass., assignor to Polaroid Corporation, Cambridge, Mass.

No Drawing. Original application June 4, 1969, Ser. No. 830,499, nowPatent No. 3,597,200. Divided and this application Oct. 23, 1970, Ser.No. 83,595

Int. Cl. C07f 11/00 U.S. Cl. 260-438.5 R 3 Claims ABSTRACT OF THEDISCLOSURE Novel metal-complexed azomethine dyes which are also silverhalide developing agents, novel non-complexed azomethines useful in thepreparation of the same, and novel photographic systems and proceduresemploying the aforementioned metal complexes to obtain color images,particularly systems and procedures for preparing color images bydiffusion transfer.

This application is a divisional of U.S. patent application Ser. No.830,499 filed June 4, 1969, now U.S. Pat. No. 3,597,200.

BACKGROUND OF THE INVENTION U.S. Pat. No. 2,983,606, issued to Howard G.Rogers, discloses diffusion transfer processes for forming color imageswherein a photographic element comprising an exposed silver halideemulsion is developed in the presence of a dye developer (dye which isalso a silver halide developing agent) to impart to a superposedimage-receiving layer a reversed or positive dye image of the developedimage. To obtain multicolor images, use is made of an integralmultilayer photosensitive element comprising at least two selectivelysensitized emulsion layers superposed on a single support, each emulsionlayer having a dye developer associated therewith. A suitablearrangement of this type for forming multicolor images comprises asupport carrying a red-sensitive silver halide emulsion stratum, agreen-sensitive silver halide emulsion stratum and a blue-sensitivesilver halide emulsion stratum, the emulsions having associatedtherewith, respectively, a cyan dye developer, a magenta dye deveolperand a yellow dye developer. Multilayer photosensitive elements of thisnature are described with more particularity and claimed in U.S. Pat.No. 3,345,163 issued to Edwin H. Land and Howard G. Rogers.

U.S. Pat. No. 3,218,165, issued to Milton Green and Leon E. Rubin,discloses that dye developers which form stable coordination complexeswith metals may be complexed to provide for use in the aforementionedsystems dye developers exhibiting increased stability against the colordegradation effects of actinic radiation, humidity and/or temperaturevariations.

The copending application of Elbert M. Idelson, Ser. No. 486,853, filedSept. 13, 1965, now U.S. Pat. No. 3,453,107, discloses a class of 1:1chrome-complexed azo dye developers for use in the aforementionedprocesses for forming color transfer images. A preferred group of thesedyes are 1:1 chromium-complexed hydroxynaphthylazo-pyrazolones whichhave been found to be particularly useful magenta dye developers to beassociated with a green-sensitive emulsion layer in the aforementionedmultilayer elements.

The present invention is directed to another class of metal-complexeddyes for use in difiusion transfer color processes such as are describedin the aforementioned U.S. patents.

SUMMARY OF THE INVENTION The present invention is directed to 1:1chromecomplexed azomethine dye developers for use in preparingmonochromatic or multicolor diffusion transfer images.

ice

The preferred complexes constitute yellow dye developers which may beused in association with the blue-sensitive emulsion in theaforementioned multilayer elements.

As was mentioned previously, this invention relates to colorphotography, and more particularly, to metal-complexed azomethine dyeswhich are also silver halide developing agents and to photographicproducts, processes and compositions employing the same to obtain colortransfer images.

A primary object of this invention, therefore, is to provide novelmetal-dye complexes.

Another object is to provide novel 1:1 chromiumcomplexed dyes.

Still another object is to provide novel metal-complexed azomethine dyescontaining a single coordinated metal atom per molecule of dye.

Yet another object is to provide novel photographic products, processesand compositions utilizing the aforementioned dyes to obtain images incolor.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the several steps and the relationand order of one or more of such steps with respect to each of theothers, and the product possessing the features, properties and therelation of elements which are exemplified in the following detaileddisclosure, and the scope of the application of which will be indicatedin the claims.

For a fuller understanding of the nature and objects of the invention,reference should be had to the following detailed description.

The metal-dye complexes to which this invention is directed are 1:1chromium-complexed azomethine dyes, i.e., dyes containing a singlecoordinated chromium atom per molecule of dye, the dye complexes beingfurther characterized by containing a silver halide developing function,preferably a p-dihydroxyphenyl silver halide developing function, aseither a part of the dye molecule, i.e., an azomethine dye developer; orcontained on the ligand moiety employed in preparing the dye complex; orboth, as will be more apparent hereinafter.

The novel dye complexes of this invention may be represented as being1:1 chromium-complexed azomethine dyes within one of the followingformulae:

wherein: A is a phenyl or naphthyl radical; B is a phenyl, naphthyl orheterocyclic radical, e.g., a pyr-azolyl radical, said comprising theradical of an ortho, ortho'-dihydroxy-azomethine dye of the formula:

including azomethine dye developers, i.e., azomethine dyes wherein the Aand/or B moieties contain a silver halide developing substituent; Xrepresents the atoms necessary to complete an aliphatic, aromatic orheterocyclic ring, preferably the atoms necessary to complete a or a 6-membered aliphatic ring or a benzene ring, which benzene ring may besubstituted and may contain a radical comprising a silver halidedeveloping function; R is alkyl, fiuoroalkyl, alkoxyalkyl, the alkylmoiety preferably being lower alkyl, phenyl, phenylamino, or a radicalcomprising a silver halide developing function; R is alkyl, fluoroalkyl,alkoxyalkyl, the alkyl moiety preferably being lower alkyl, phenyl, orphenylamino; R may be hydrogen, lower alkyl, phenyl, or a radicalcomprising a silver halide developing function; and R may be loweralkyl, hydroxyl, hydrogen, or a radical comprising a dihydroxyphenylsilver halide developing function, provided that where X represents theatoms necessary to complete an aromatic ring, R cannot be hydroxyl; andprovided further that at least one of said moieties which may contain orcomprise a dihydroxyphenyl silver halide developing function does so,i.e., that at least one developing function is contained on the dyemolecule and/or the ligand moiety contributing the two oxygen atomsbonded to the chromium atom.

In a preferred embodiment of the invention, the ligand moiety contains asilver halide developing function. The preferred 1:1 complexes of thisinvention may, therefore, be defined as being complexes within one ofthe following formulae:

(D) A--CH=N n ACH=N and (G) A-CH=N B wherein A, B, and R have themeanings heretofore given (the A and/or B moiety may also contain asilver halide developing function, as heretofore mentioned), R isalkylene, preferably lower alkylene, phenylene, phenylamino, or asubstituted derivative thereof; R is alkylene, preferably loweralkylene, R is hydrogen, alkyl, preferably lower alkyl, alkoxyalkyl,alkylamino, phenyl, phenylamino, or a substituted derivative thereof; Ris lower alkyl, hydroxyl or hydrogen, R is hydrogen, lower alkyl orphenyl; X represents the atoms necessary to complete a five or asix-membered aliphatic ring or a benzene ring; and Y s a radical cmprising a silver halide developing 4 1 a substituent, preferably ap-dihydroxyphenyl silver halide developing substituent. As usedthroughout the specification and claims, the term lower alkyl refers toalkyl substituents containing 1-6 carbon atoms, e.g., methyl, ethyl,propyl, isopropyl, butyl, isobutyl, pentyl, .hexyl, etc.

As examples of silver halide developing substituents, mention may bemade of phenyl or naphthyl nuclei containing at least a hydroxy and/ oramino substituent ortho or para to another such substituent. Silverhalide developing substituents of the foregoing description are per sewell known in the field of photography (see, for example, Photography,Its Materials and Processes, 6th edition, by Neblette, published by D.van Nostrand Company, Inc., (1962), pp. 231-234). A preferred group ofdeveloping substituents are the hydroquinonyls, including substitutedderivatives thereof, e.g., chloro, methyl, phenyl, and/ormethoxy-substituted derivatives of hydroquinone. As examples of usefulsubstituted hydroquinones, mention may be made of the following:methylhydroquinone; p-methylphenyl hydroquinone; chlorohydroquinone;methoxy hydroquinone; 2,6-dimethyl-hydroquinone;2,-dimethoxyhydroquinone; 2 methoxy-6- methyl-hydroquinone;2,3-dimethylhydroquinone; 2,5,6- trimethyl-hydroquinone, etc., all ofwhich are per se known in the art.

In addition to the above-mentioned substituents contributing to thesilver halide developing function, the benzene or naphthalene nucleusmay contain other substituents for linking the developing moiety to theligand moiety. As examples of such linking substituents, mention may bemade of aminophenalkyl-thio substituents such as disclosed in U.S. Pat.No. 3,009,958; aminoalkylamino substituents such as disclosed in US.Pat. No. 3,002,997; aminophenalkyl substituents such as disclosed in US.Pat. No. 3,019,107; alkyl-thio substituents such as disclosed in US.Pat. No. 3,043,690; aminoalkyl substituents such as described in U.S.Pat. No. 3,062,884; aminophenyl substituents such as disclosed in US.Pat. No. 3,134,811; the acyl substituents such as disclosed in US. Pat.No. 3,142,564; the arninophenoxy substituents such as disclosed in US.Pat. No. 3,061,434, etc., as well as the various linking substituentsdisclosed in US. Pat. No. 3,255,001.

The preferred azomethine dyes contemplated by the present invention areyellow dyes of the formula:

wherein the alkoxy moiety contains 1-5 carbon atoms, e.g., methoxy,ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and pentoxy; n and m arepositive integers from 1-2. The nitro substituent (or substituents) is(are) preferably meta to the nitrogen linkage. Where in is two, thealkoxy substituents are preferably the same and are substituted in theortho and para positions, respectively. In the most preferred yellowazomethines, n is 1 and m is 2. The respective benzene groups may alsocontain other substituents contributing to the spectral, physical and/orchemical properties of the dye, as will be appreciated by those skilledin the art. They may, for example, contain hydroxyl, amino or carboxysubstituents.

-As examples of azomethine dyes useful in the preparation of the novelcomplexes of this invention, mention may be made of the following:

CH=N 2]; (5H

(25) (a9) N0 7 No,

GH-TNQ-Q 10 onto 7 SE ()B (26) Where not readily available, thenon-complexed am- I 1 methine dye may be obtained by reacting analdehyde of (GHQrNQ H'L-y the general formula: v

| a t A-CHO on H H (27) wherein the hydroxy group is ortho to thealdehyde sub (CIHPN OH=N N0 stituent, with an amine of the generalformula:

H 23 OCH NO I v wherem the hydroxy group 15 ortho to the amine sub- CH'OHzN stituent, to obtain an azomethine dye of Formula C.

25 Where the dye moiety includes a dihydroxyphenyl sil- H H ver halidedeveloping substituent, it may be desirable to use its protectedderivative form, e.g., diacyloxy, di- N0! benzyloxy, dicathyloxy, etc.,in which event, the desired dihydroxy substituents may be readilyobtained by hy- (CHQIN CH=N 30 drolysis in accordance with proceduresheretofore known in the art for preparing the developers. H H Apreferred method for preparing the novel complexes (30) of thisinvention is to react the non-complexed dye, i.e., ma dye of Formulae Cor H, with a suitable chromic salt,

e.g., chromic acetate, chromic chloride, etc. and the de- E H siredligand to be described with more particularity here- (a!) NO, matter.

i The ligands or coordination agents employed to form CH=N the metalcomplexes of this invention may be defined asfl-hydroxy-a,fl-unsaturated carbonyl compounds, or com- H pounds capableof tautomerizing to such a structure. As was mentioned previously, thedeveloper moiety may be (32) 00,1 0, contained on the dye molecule; itmay be contained on i the ligand moiety; or on both. Hence, where thedye 0,1350 CH=N molecule contains a developer moiety, i.e., is a dyedeveloper, the ligand need not contain a developer. Those H H fligandswhich need not contain a developer and which may be employed in thepractice of this invention may be (33) represented by the followingformulae: rimean, cn=u (I) Y o o Y I ma mas H H y (s4 0 :H1n N andn-oamo CH=N I 0 v I 3 E x 3. v -x-' (35) bon -n wherein: all symbolshave the meaning heretofore given in connection with thedescription ofFormulae A and B. n-onno CH=N As examples of useful ligands withinFormulae I and v v I, mention may be made of the following:

a H H o 0 I ll (36) c lq'o, CHa--CHrC-CH; u nQ- CII N (I) (I) CH -CH&CH;;( J-OH;

n c N o 0 (37) Game en onrl z-om-li-cnr-ona (CHg):CHdHa6C C =N O O Icrw-kom-d-c F,

Those ligands containing a silver halide developing function(developer-ligands) ,may be represented by the following forrnulae:

wherein: all symbols have the meanings described in con- 1 nection withthe discussion of Formulae D-G.

As examples of useful developer-ligands, mention may be made of thefollowing:

0 I] (H) O-o-om-on 0 ll @CEh-C-CHz-C-CH:

Developer-ligands of the foregoing desciption are described and claimedin the copending application of Elbert M. Idelson, Ser. No. 487,054,filed Sept. 13, 1965, now abandoned, and per se comprise no part of thisinvention.-

In some instances it may be desirable to employ the protected form ofthe developer ligand, e.g., ligands wherein the hydroxy groups arereplaced by acyloxy, benzyloxy, cathyloxy, alkoxy or acetoxysubstituents, in which case the metal-complexed dye may be converted tothe dihydroxyphenyl silver halide developing agentcontaining ligand'developer'by hydrolysis, e.g., with a suitable mineral acid, at somestage after complexing.

The preferred metal complexes of this invention are those formed bycomplexing an azomethine of Formula H with a developer-ligand ofFormulae K, L, M or N.

, 12 I complexed azomethine dye developers of this invention 1 1 Thesepreferred complexes may be represented as being within one of thefollowing formulae:

(or protected derivative thereof):

I (alk'oxyh (Noon (alkdxy):

and

H H .m V m n w 7 m {\OHC A v m A w m 0 V V o y w t or m m w w m "w. w m

' The following are illustrative or the novel lzl chrome- OH gi l-omen,-

O [*OH,

It will be noted that the complexes of Formulae 48-52 are protectedderivatives, the desired dihydroxyphenyl' analogue being readilyobtainable by hydrolysis, as previously mentioned.

As was mentioned previously, azomethine dyes useful in the preparationof the metal complexes of this invention may be obtained by reacting thedesired aldehyde with an amine.

Thus, for example, the preferred azomethines of Formula H may beobtained by the following reaction:

momma-Q4110 NH -Q-(NOQJ Dye H no The following examples illustrate thepreparation of azomethine dyes within the scope of Formula H.

Example 1 Example 2 In the manner described in Example 1, 2-hydroxy-4,6-

diisopropoxy-benzaldehyde and 2-hydroxy-5-nitro-aniline were reacted toyield the azomethine dye of Formula 33, M.P. 243 C.

In like manner were prepared the compounds of Formule 22, M.P. 276-2765;Formula 23, M.P. 194-195; Formula 24, M.P. 303-4; Formula 28, M.P.282-3; Formula 32, M.P. 247-8; Formula 34, M.P. 233-4; Formula 35, M.P.228-9; Formula 36, M.P. 208-9; and Formula 37, M.P. 232-3, all meltingpoints given in C.

To prepare the metal complexes of this'invention, the azomethine dye,e.g., a dye as prepared in the above examples, may be reacted with achromic salt and the desired ligand. In instances wherein the developeris on the li a nd, the protected derivative thereof, e.g., thedicathyloxy analogue, is preferably employed to yield the correspondingchrome complex wherein the dihydroxy substituents are protected. Thedesired dihydroxy analogue is then obtained by hydrolysis.

This series of reactions may be illustrated as follows:

[intermediate] 2 o ocooon n 2 I ii-cn -cn [intermediate 'i' 1 I(anoxy)..Qon- -n @-moa Kl/O/ i -0111 a 1 (f ocooczng fih-on on OH", Hs

(nmynQcn=N -(No,m

(Jr-0H, o o .orr ffi-l-cm-en The following examples illustrate thepreparationof the chrome complexes of this invention in accordance withthe foregoing sequence of reactions.

Example 3 l 0.06 m. of the azomethine of Formula H and 0.12 m. (32 g.)of CrCl ,6H O were refluxed in 1 liter of methanol for 72 hours. 0.09 m.(36 g.) of the protected liganddeveloper (III) and 90 ml. oftriethylamine were then added and the resulting slurry was refluxed for1 hour and poured while still hot into a solution of 3 1. water/ 90 ml.cone. HCl. The resulting gummy product solidified on trituration and thecloudy supernatant liquid was decanted 01f. The product was washedseveral times with water by decantation, filtered oil? and air-dried toyield the pro- Ite'cted chrome complex (IV). This complex was dissolvedin 500ml. of methyl Cellosolve by warming on a steam bath. The solutionwas cooled to room temperature and deaerated with nitrogen for 15-20minutes. A deaerated solution of 36 ml. each of 50% W/ W aqueous sodiumhyxdroxide solution and water was added all at once, producof hot'methyl Cellosolve, and again filtered. 1 liter of a hot filteredsolution of 1% HCl was poured into the above filtrate. A gummy productsoon solidified and the supernatant liquid was decanted 01f. Thisproduct was washed several times with hot water by decantation, finallysucked dry and dried in vacuo. It was then dissolved in 500 ml. of warmacetone, the solution was filtered, and 1.5 l. of

Example 4 In the manner described in Example 3, the chromecomplexed dyeof Formula 59 was prepared, a yellow dye developer, A =400, e=18,600; A=440, e=17,- 400 in methyl Cellosolve.

Example 5 In like manner, the chorme-complexed dye of Formula 58 wasprepared, A =400, e=18,400; k =440, e=17,200 in methyl Cellosolve.

Example 6 In like manner, the chrome-complexed dye of Formula- 60 wasprepared, A ='-400-4l0, e=20,400; M :440, e=19,400 in methylCellosolve.

The following examples illustrate the use of the novel complexed dyes ofthis invention in color photography.

Example 7 The dye complex of Example 6 was precipitated from methylCellosolve into distilled water at a pH of about 1. The resultingprecipitate was washed ten times and collected each time by means of acentrifuge. To the resulting paste was added 10% by weight (based on dyesolids) of Lomar D (trademark of Nopco Chemical Co. for a sodium salt ofa condensedmononaphthalene sulfonic acid dispersant) and a high shearmechanical agitator was then applied to form a dispersion. 10 cc. of theresulting dye dispersion (containing about 1.0 g. of dye) were mixedwith 7.7 g. of 15%: gelatin, 26.2 cc. of water and 2.8 cc. of 1% AerosolO.T. (trademark of American Cyanamid for dioctyl ester of sodiumsulfosuccinic acid wetting agent) and this mixture was then coated upona subcoated film base at a calculated dry coverage of about l03 mg. ofcomplexed dye developer per square foot of surface area. After thiscoating dried, a bluesensitive silver iodobromide emulsion was coatedthereupon at a coverage of about mg. of silver per square foot ofsurface area. The resulting photosensitive element was exposed and thethus exposed element was then processed by spreading between the exposedphotosensitive element and a superposed image-receiving element at a gapof about .0026 inch an aqueous processing composition comprising thefollowing proportion of ingredients:

The image-receiving element comprised a baryta paper support carrying,in order, a layer'of a partial butyl ester of poly-(ethylene/maleicanhydride); a layer of polyvinyl alcohol; and a layer of a 2:1 mixture,by weight, of polyvinyl alcohol and poly-4-vinylpyridine.[Image-receiving elements of this type are disclosed in US. Pat. No.3,362,- 819 issued to Edwin H. Land] After an imbibition period of about60 seconds, the two elements were separated to reveal a yellow transferimage having a D of 1.90.

The novel chrome-complexed azomethines of this invention exhibitmarkedly greater stability against the color degradation elfects ofactinic radiation than do noncomplexed dyes of similar color. This isconsistent with the knowledge of those skilled in the art that dyecomplexesare more light stable, e.g., fade less or are less prone tocolor shift, than non-complexed dyes.

On the other hand, the present invention provides dyes possessing acolor which makes them superior to prior dye complexes for multicolorphotography. Thus the metal-complexed yellow dye developers of thisinvention give more faithful color. recordation in multicolorphotographic elements such as mentioned above including a yellow dyedeveloper, a magenta dye developer and a cyan dye developer, than theheretofore known metalcomplexed yellow dye developers. Stated anotherway, the metal-complexed yellow azomethines of this invention havesuperior spectral absorption curves giving less absorption in unwantedregions of the spectrum than do prior complexed yellow dye developers.

In summation, the yellow dye developers of this invention are morestable than prior non-complexed yellow dye developers and maybe ofsuperior color; while on the other hand, they possess a better color formulticolor photography than prior complexed yellow dye developers,although they are not necessarily more stable than these prior yellowcomplexes. It will thus be seen that the present invention combinesdesirable features of prior yellow dye developers not heretoforeobtainable to provide dye developers which, considering the combinedfeatures of color and "stability, are superior to those heretoforeknown.

The foregoing may be illustrated by comparing illutrative yellow dyedevelopers of this invention with (I) a typical yellow complex of theprior art, the chromium complex of the yellow azo dye:

COOH HO N HgCH and (II) a standard test or control non-complexed yellowdye developer employed in evaluating the merits of yellow dyedevelopers:

cm-onQ-rwu In order to do so, color images employing each of these dyedevelopers were prepared under test conditions using standard controlsso that the only essential difference in the three was the particulardye developer employed. In this instance, for each of the yellow dyedevelopers to be compared, a photosensitive element comprising anemulsion layer and the dye developer layer was exposed and developed inthe manner described in Example 7.

The resulting three dye images were subjected to a standard lightstability test by placing under a Xenon arc weatherometer forpredetermined periods of time and calculating the percent of fading(loss of density) after each period of time.

The results comparing two of the yellow dye developer complexes of thisinvention with the aforementioned azo 4.2 yellow dye developer complexand control non-complexed dye developer are shown in the followingtable.

As far as color is concerned, the dye developers of formulae 59 and 60were both superior to the azo yellow complex and non-complexed yellowcontrols, particularly in that the dye developers of this invention bothexhibited substantially greater of the desired absorption in the blueregion of the spectrum.

The dye developers of this invention are also quite stable to pH change.Thus, for example, whereas the aforementioned non-complexed yellow is pHsensitive and at a pH of between 57 shifts bathochromically towards theorange, the present dye developers do not.

The dye complexes of this invention are also useful in integralmultilayer photosensitive elements for use in multicolor diffusiontransfer processes. As an example of such photosensitive elements,mention may be made of the photosensitive elements disclosed and claimedin U.S. Pat. No. 3,345,163 of Edwin H. Land and Howard G. Rogers,wherein at least two selectively sensitized photosensitive strata aresuperposed on a single support and are processed, simultaneously andwithout separation, with a single common image-receiving element. Asuitable arrangement of this type comprises a support carry ing ared-sensitive silver halide emulsion stratum, a greensensitive silverhalide emulsion stratum and a blue-sensitive silver halide emulsionstratum, said emulsions having associated therewith, respectively, acyan dye developer, a magenta dye developer and a yellow dye developer.In one of the preferred embodiments of photosensitive elements ofthistype, the dye developers are disposed in separate alkali-permeablelayers behind the photosensitive silver halide emulsion stratum withwhich they are associated.

They may also be employed, for instance, in photosensitive elements ofthe type disclosed in U.S. Pat. No. 3,414,644 issued to Edwin H. Land.

The photosensitive elements within the scope of this invention may beused in film units which contain a plurality of photosensitive frames.The photosensitive ele ments of this invention are especially useful incomposite film pack and roll film structures intended for use in aPolaroid Land Camera, sold by Polaroid Corporation, Cambridge, Mass.02139, or a similar camera structure such, for example, as the film packtype camera shown in U.S. Pat. No. 2,991,702, issued to Vaito K.Eloranta on July 11, 1961, or the roll film type camera forming thesubject matter of U.S. Pat. No. 2,435,717, issued to Edwin H. Land onFeb. 10, 1948. In general, such composite roll films comprise aphotosensitive roll, a roll of imagereceiving material and a pluralityof pods containing an aqueous alkaline processing solution. The rollsand pods are so associated with each other that, upon processing, thephotosensitive element may be superposed on the image-receiving elementand the pods may be ruptured to spread the aqueous alkaline processingsolution be tween the superposed elements. The nature and construc tionof the pods used in such units are well known to the art. See, forexample, U.S. Pats. Nos. 2,543,181 and 2,634,886, issued to Edwin H.Land.

It will be noted that the liquid processing composition may contain oneor more auxiliary or accelerating silver halide developing agents, suchas p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol);benzylarninophenol; hydroquinones, a substituted hydroquinone such astoluhydroquinone, phenylhydroquinone, or 4'-methyl- 23phenylhydroquinone; or a 3-pyrazolidone such as lphenyl-3-pyrazolidone.These silver halide developing agents are substantially colorless, atleast in their unoxidized form. It is possible that some of the dyedeveloper oxidized in exposed areas may be oxidized by an energytransfer reaction with oxidized auxiliary developing agent.

In addition, development may be effected in the presammoniurn compound,in accordance with the processes disclosed and claimed in US. Pat. No.3,173,786, issued to Milton Green and HowardG. Rogers on Mar. 16, 1965,and/or with a coupler in accordance with the processes disclosed andclaimed in the copending application of Howard G. Rogers, Ser. No.455,302, filed May 12, 1965, now US. Pat. 3,502,468.

The dye complexes of this invention may be used also inconventionalphotographic processes, such as tray or tank development of conventionalphotosensitive films,

. plates or papers to obtain black-and-white, monochromatic or tonedprints or negatives. By way of example,

' a developer composition suitable for such use may comprise an aqueoussolution of approximately 12% of the dye, 1% sodium hydroxide, 2% sodiumsulfite and 0.05% potassium bromide. After development is completed, anyunreacted dye is soluble. The expression toned is used to designatephotographic images wherein the silver is retained with the precipitateddye, whereas monochromatic is intended to designate dye images free ofsilver.

- of special photographic materials,'for example, film materials of thetype containing two or more photosensitized elements associated with anappropriate number of image-receiving elements and adapted to be treatedwith one or more liquid processing compositions, appropriate dyedevelopers suitable to impart the desired subtractive I colors beingincorporated in the photosensitized elements or in the liquid processingcompositions. Examples of such photographic materials are disclosed inUS. Pat. No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, mention may be made ofnylon, c.g., N-methoxymethyl-polyhexamethylene adipamide, polyvinylalcohol, and gelatin, particularly polyvinyl alcohol or gelatincontaining a dye mordant such as poly-4-vinylpyridine. Theimage-receiving element also may contain a development restrainer, e.g.,

l-phenyl-S-niercaptotetrazole, as disclosed in US. Pat. No. 3,265,498 ofHoward G. Rogers and Harriet W. Lutes.

The dye complexes herein set forth are also useful in the formation ofcolored images in accordance with the photographic products andprocesses described and claimed in US. Pat. No. 2,968,554, issued toEdwin H. Land on Ian. 17, 1961. r The novel complexes herein disclosedare alsosuitable for use as dyes for textile fibers, such as nylor1'.'-

In the preceding portions of the specification, the expression ,colorhas been frequently usedil'his expression is intended to include the useof a plurality of colors to obtain black. I

' Since certain changes may be made in the above products, compositionsand processes without departing from the scope of the invention hereininvolved, it is intended that all matter contained in the abovedescription shall be interpreted as illustrative and not in a limitingsense.

' ence of an onium compound, particularly a quaternary 24 What isclaimed is: 1. A 1:1. chrome complexed azomethine dye within theformulae:

and

0 (l) ll I s -xa wherein A is a phenyl or naphthyl nucleus, B is aphenyl or a naphthyl radical, said is the radical of an ortho,ortho-dihydroxy-azomethine dye of the formula:

ACH=NB X represents the atoms necessary to complete an aliphatic oraromatic ring, R and R are each selected from the group consisting ofalkyl, fluoroalkyl, alkoxyalkyl, phenyl, and phenylamino radicals, R isselected from the group consisting of hydrogen and alkyl and phenylradicals and R is selected from the group consisting of hydrogen,

- lower alkyl and hydroxyl, provided that when X represents the atomsnecessary to complete an aromatic ring, R is selected from the groupconsisting of hydrogen and lower alkyl radicals.

2. The compound as defined in claim 1 wherein each of said A and Bmoieties comprises a benzene nucleus.

3. A 1:1 chrome-complexed azomethine dye as defined in claim 1, saidcomplex being within the formulae:

A-C H:

and

A-CII=N B wherein R is selected from the group consisting of al- 10 26drogen, R is hydrogen, alkyl or phenyl, X represents the atoms necessaryto complete a 5 or a 6-membered aliphatic ring or a benzene ring and Yis a radical comprising a p-dihydroxyphenyl silver halide developingsubstituent.

References Cited UNITED STATES PATENTS 2,116,913 5/1938 Schmidt 260429 CHELEN M. S. SNEED, Primary Examiner US. Cl. X.R. 9629, 93

